Method and composition for textile printing

ABSTRACT

The present invention features novel methods and compositions for coating textile substrates, wherein the coating compositions are composed of a coating agent selected from one of (a) an azetidinium polymer, (b) a guanidine polymer, (c) a mixture of an azetidinium polymer and a guanidine polymer, and (d) a copolymer of an azetidinium monomer and a guanidine monomer. Textile substrates coated with the compositions provide high quality printed images when printed with an ink containing a reactive dye having ionizable and/or nucleophilic groups capable of reacting with the coating agent in the textile coating composition. Images printed on a textile substrate coated with a coating composition of the invention are bleed-resistant, water-resistant (e.g., water-fast), detergent-resistant (e.g., detergent-fast), and/or are characterized by an enhanced chroma and hue.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. provisional patent application60/082,697, filed Apr. 22, 1998.

TECHNICAL FIELD

The present invention is directed to treatment of textiles, and moreparticularly relates to a method and composition for treating textilesto improve the quality of images printed thereon.

BACKGROUND

Current textile printing technologies are deficient in meeting modern,time-driven, demand-responsive manufacturing strategies. In general, theconventional method of printing on textiles involves crosslinking acolorant to the cellulosic fiber of the textile itself. This approach islimited in that it relies on processes that involve multiple,time-consuming steps. Furthermore, the types of substrates and colorantsthat can be used are limited.

One approach for increasing textile printing speed involves the use ofinkjet printing. Inkjet printers are very popular, due at least in partto their reliability, relatively quiet operation, versatility, graphicscapability, print quality, and low cost. Moreover, inkjet printers havemade possible “on demand” color printing without the need forcomplicated devices. Because inkjet printing has become so popular inboth home and commercial use, several water-soluble inks are available.The inks are typically composed of water and a colorant, usually a dyeor pigment dispersion, and often contain a number of additives forimparting certain features to the ink, e.g., improved stability andflow, smear resistance, and the like.

Unfortunately, the use of inkjet printing techniques to print ontextiles has met with several problems. First, and in spite of the largenumber of inkjet inks currently available, inkjet printed images ontextiles are often of low quality. For example, the printed images oftensmear upon handling, exhibit bleed (the intrusion of one color into anadjacent color), are moisture sensitive, and are dull, i.e., coloredinks when printed fail to accurately produce the expected hues.Moreover, the printed images are often neither water-fast nordetergent-resistant, resulting in fading of the printed image afterwashing. Printed textile images with these drawbacks are whollyunacceptable to the textile industry, which requires not only that theimage be both water-resistant and detergent-resistant, but also that thecolors and hues are those deemed acceptable in the textile field. Inaddition, the textile industry also demands that while the colorant ofthe ink must adhere tenaciously to the substrate, it also must not alterthe desirable hand properties of the substrate. This combination ofrequirements is very difficult to accomplish.

Although there have been developments and improvements in the field oftextile printing, the methods currently used still do not provideoptimum results. Thus, there is a need in the art for a textiletreatment that can overcome the above problems, is relativelyinexpensive, and can generally provide a high quality inkjet printedimage on a textile substrate, preferably using presently available dyes.The present invention is addressed to this need.

SUMMARY OF THE INVENTION

The present invention features a novel method and composition forcoating textile substrates, wherein the composition is composed of acoating agent selected from one of (a) an azetidinium polymer, (b) aguanidine polymer, (c) a mixture of an azetidinium polymer and aguanidine polymer, and (d) a copolymer of an azetidinium monomer and aguanidine monomer. When applied to a textile substrate, the coatingcomposition provides a coated textile substrate that yields high qualityprinted images when printed with an ink containing a reactive dye havingionizable and/or nucleophilic groups capable of reacting with thecoating agent. Images printed on a textile substrate coated with thecoating composition of the invention are bleed-resistant,water-resistant (e.g., water-fast), detergent-resistant (e.g.,detergent-fast), and/or are characterized by an enhanced chroma and hue.

It is a primary object of the invention to address the above-mentionedneed in the art by providing a coating composition that can be readilyapplied to a variety of textile substrates and that efficiently bindscolorant upon printing, thus providing an economical, efficient meansfor processing textiles so as to facilitate production of a high qualityprinted image.

Another object of the invention is to provide a printed textilesubstrate that is of high quality (particularly with respect to opticaldensity and brightness of the printed image), and that isbleed-resistant, water-resistant (e.g., water-fast), anddetergent-resistant (e.g., detergent-fast).

Still another object of the invention is to provide a method for coatingtextiles using the coating compositions of the invention.

Still an additional object of the invention is to provide a method forprinting on a coated textile substrate to provide water-resistant (e.g.,water-fast) and/or detergent-resistant (e.g., detergent-fast) imagesthereon.

Additional objects, advantages and novel features of the invention willbe set forth in part in the description which follows, and in part willbecome apparent to those skilled in the art upon examination of thefollowing, or may be learned by practice of the invention.

DETAILED DESCRIPTION OF THE INVENTION Definitions and Nomenclature

It must be noted that, as used in the specification and the appendedclaimnr the singular forms “a,” “an” and “the” include plural referentsunless the context clearly dictates otherwise. Thus, for example,reference to “a colorant-reactive component” in a composition means thatmore than one colorant-reactive component can be present in thecomposition, reference to “a colorant” in a composition means that morethan one colorant can be present in the composition, reference to “apolymer” includes combinations of different polymers, and the like.

“Textile” or “textile substrate” as used herein refers to anycellulose-based or non-cellulose based textile material suitable for useas a printing substrate in connection with the coatings and/or methodsof the invention. In general, where appropriate, the textile substratehas been sized, internally and/or externally, prior to application ofthe compositions of the invention.

The terms “treated textile substrate,” “coated textile substrate,”“treated textile substrate,” and “coated textile substrate” aregenerally used herein to refer to a textile substrate that is treatedwith, i.e., has applied to its surface and/or is partially or whollysaturated with, a coating of the present invention, to provide forimproved printing performance, particularly with respect to waterresistance (e.g., water-fastness), detergent resistance (e.g.,detergent-fastness), brightness, and the like. The coating may beapplied as a pretreatment, i.e., prior to printing, simultaneously withprinting, or as an after-treatment. Preferably, the coating is appliedto the substrate in a separate coating operation prior to printing,typically in amounts ranging from fifty (50) to five hundred (500)pounds per ton of substrate. “Coating composition” as used herein isgenerally meant to refer to a composition of the invention comprised ofa coating agent as described herein. The coating composition may containcomponents in addition to the coating agents described herein, such asbinders, colorants, etc. The use of the term “coating” in the phrase“coating composition” is not limited to the presence of the compositionon a surface of a textile substrate, but is also intended to encompass atextile substrate that has been infiltrated with the composition, suchthat the composition is present within the fibers of the treatedsubstrate. Unless specifically indicated otherwise, “coating” inreference to the coating compositions and coating agents of theinvention is used only as a term of convenience, and is not meant to belimiting as to the manner of application of the compositions of theinvention, or their final location on and/or within a treated textilesubstrate.

“Aqueous based ink” refers to an ink composed of an aqueous carriermedium and a colorant, such as a dye or a pigment dispersion. An aqueouscarrier medium is composed of water or a mixture of water and one ormore water-soluble organic solvents. Exemplary aqueous based inkcompositions are described in detail below.

“Colorant” as used herein is meant to encompass dyes, pigments, stains,and the like compatible for use with the coating agents and compositionsof the invention.

The term “colorant-reactive component” as used herein refers to acomponent (e.g., a chemical moiety) of a coating agent of the inventionthat is capable of reacting with a selected colorant, particularly acolorant having a nucleophilic and/or ionizable group, to form a coatingagent-colorant complex. The coating agent-colorant complex is formedthrough either a covalent, electrostatic, or ionic association betweenthe colorant-reactive coating agent and the colorant. When a coatingagent having a colorant-reactive component and a selected colorant forma coating agent-colorant complex in the context of a printed image on atextile substrate, the association between the colorant and thecolor-reactive component of the coating agent is effective to impartadvantageous qualities to the printed image on the textile substrate,particularly with respect to water resistance, detergent resistance,enhanced optical density, enhanced brightness, and the like.

The term “organic solvent” is used herein in its conventional sense torefer to a liquid organic compound, typically a monomeric organicmaterial in the form of a liquid, preferably a relatively nonviscousliquid, the molecular structure of which contains hydrogen atoms, carbonatoms, and optionally other atoms as well, and which is capable ofdissolving solids, gases or liquids.

The term “significant”, as when used with reference to “significantlyenhanced brightness” or “significantly improved water resistance”generally refers to a difference in a quantifiable, measurable, orotherwise detectable parameter, e.g., optical density, LAB graphs (colorsphere), dot spread, bleed through, between the two groups beingcompared (e.g., untreated versus treated textile substrates) that isstatistically significant using standard statistical tests. For example,the degree of visual wicking or water resistance in a treated textilesubstrate as detected in a print assay may be quantified using standardmethods, and the degree of wicking or water resistance under differentconditions can be compared for both treated and untreated textilesubstrates to detect statistically significant differences.

The term “fluid resistance” is used herein to describe the resistance ofa textile substrate to penetration by a fluid, with the term “waterresistance” specifically referring to resistance of a textile substrateto penetration by a fluid.

The term “water-fast” is used herein to describe a form of waterresistance, and is normally used to refer to the nature of the inkcomposition after drying on a substrate. In general, “water-fast” meansthat the dried composition is substantially insoluble in water, suchthat upon contact with water, the dried ink retains at least about 70%,preferably at least about 85%, and more preferably at least about 95%,of optical density.

The term “detergent-resistant” is used herein to describe the nature ofthe ink composition after exposure to detergent (e.g., during washing).“Detergent-fast” is intended to refer to a particular high-level of“detergent resistance,” and is generally used to mean that the driedcomposition is substantially insoluble in water, such that upon contactwith water, the dried ink retains at least about 70%, preferably atleast about 85%, and more preferably at least about 95%, of opticaldensity.

The term “bleed resistance” is meant to refer to the retardation of thepenetration of water into a textile substrate, which retardation isassociated with creation of a low energy hydrophobic surface at thetextile fiber-water interface which increases the contact angle formedbetween a drop of liquid and the surface, and thus decreases thewettability. Contact angles have been shown to be sensitive to molecularpacking, surface morphology, and chemical constitution of the textilesubstrate and any components added thereto.

The term “rub resistance” is normally meant to refer to a characteristicof the ink composition after drying on a substrate, more specifically,the ability of a printed image to remain associated with the substrateupon which it is printed despite application of force (e.g., rubbing) tothe printed image. In general, “rub-resistant” means that the dried inkcomposition is substantially resistant to rubbing force so that thedried ink retains at least about 70%, preferably at least about 85%, andmore preferably at least about 95%, of optical density after rubbing ofthe printed image.

The term “alkyl” as used herein refers to a branched or unbranchedsaturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl,tetradecyl, hexadecyl, eicosyl, tetracosyl and the like, as well ascycloalkyl groups such as cyclopentyl, cyclohexyl and the like. The term“lower alkyl” intends an alkyl group of 1 to 6 carbon atoms, preferably1 to 4 carbon atoms.

The term “alkylene” as used herein refers to a difunctional, branched orunbranched saturated hydrocarbon group of 1 to 24 carbon atoms,including without limitation methylene, ethylene, ethane- 1,1-diyl,propane-2,2-diyl, propane-1,3-diyl, butane- 1,3-diyl, and the like.“Lower alkylene” refers to an alkylene group of 1 to 6 carbon atoms.

The term “alkoxy” as used herein intends an alkyl group bound through asingle, terminal ether linkage; that is, an “alkoxy” group may bedefined as —OR where R is alkyl as defined above. A “lower alkoxy” groupintends an alkoxy group containing 1 to 6 carbon atoms.

“Halo” or “halogen” refers to fluoro, chloro, bromo or iodo, and usuallyrelates to halo substitution for a hydrogen atom in an organic compound.

The term “polymer” is used herein in its conventional sense to refer toa compound having two or more monomer units, and is intended to includehomopolymers as well as copolymers. The term “monomer” is used herein torefer to compounds which are not polymeric.

“Optionally” or “optionally” means that the subsequently described eventor circumstance may or may not occur, and that the description includesinstances where said event or circumstance occurs and instances where itdoes not. For example, the phrase “optionally substituted” aromatic ringmeans that the aromatic ring may or may not be substituted and that thedescription includes both an unsubstituted aromatic ring and an aromaticring bearing one or more substituents.

Overview of the Invention

The present invention is based upon the discovery that a coatingcomposition containing a coating agent that is (a) an azetidiniumpolymer, (b) a guanidine polymer, (c) a mixture of an azetidiniumpolymer and a guanidine polymer, or (d) a copolymer of an azetidiniummonomer and a guanidine monomer, can be used to treat a textilesubstrate to significantly improve the quality of images printedthereon. Textile substrate that has been treated with a coating agent ofthe invention can provide high quality printed images having improvedcolor fastness, that is, the printed images do not run when exposed tomoisture and/or detergent, as a result of the substantiallynon-reversible binding of aqueous colorants to the image-enhancing agentpresent in the image-enhancing composition. These images are thereforecharacterized as “water-resistant” (e.g., water-fast) and/ordetergent-resistant (e.g., detergent-fast) due to the characteristics ofthe printed image following exposure to water and/or detergent.

The coated textile substrates of the invention can be used withconventional textile printing processes, or may be used with digitalprinting techniques such as inkjet printing (including drop-on-demandprinting and continuous printing), to provide highly brilliant, printedimages that are significantly improved in color quality, for example,with respect to chroma and hue. The coating agents and compositions ofthe invention thus provide a number of advantages over conventionaltextile printing methods.

The coating agents, compositions, methods of treating textile substratesusing the compositions described herein, and other features of theinvention are described in greater detail below.

Coating Compositions

In general, the coating composition of the invention is composed of acoating agent selected from the group consisting of (a) an azetidiniumpolymer, (b) a guanidine polymer, (c) a mixture of an azetidiniumpolymer and a guanidine polymer, and (d) a copolymer of an azetidiniummonomer and a guanidine monomer. In general, the coating agents have acolorant-reactive component, which is capable of reacting with aselected colorant, particularly a colorant having a nucleophilic and/orionizable group, to form a coating agent-colorant complex through acovalent, electrostatic, or ionic association. The association of thecoating agent and colorant imparts bleed resistance, water resistance(e.g., water-fastness), detergent resistance e.g., detergent-fastness),and other desirable characteristics to the printed, treated textilesubstrate. In addition to the coating agent, the coating compositionscan include components such as film-forming binders, pigments, and otheradditives.

In general, the compositions can be readily prepared from commerciallyavailable starting materials and/or reagents, are compatible withadditional binders or additives, can be used with a variety of basetextile substrates, are compatible with a variety of printing methods,including conventional textile printing as well as digital printingmethods (particularly inkjet printing, including drop-on-demand andcontinuous printing), and can also be used with existing commercialtextile coating processes and equipment. The coating compositions areinexpensive to prepare, and relatively small amounts are required toprovide a coated textile substrate having the advantageous featuresdescribed herein. The coating compositions are also easy to handle dueto their solubility in water (the active coating agents are hydrophilicpolymers), and do not require the use of large volumes of organicsolvents. The coating compositions also possesses good film-formingproperties.

The treated textile substrates prepared using the coating compositionsof the invention exhibit improved stability upon prolonged storage, andin some instances, improved durability, as evidenced by improvedstrength, e.g., tear strength. The treated textile substrate does notdiscolor or yellow, and maintains a high degree of brightness forextended periods of time. Textile substrates treated with the coatingcompositions of the invention react rapidly with a number of aqueousbased colorants, thus providing a versatile coating system for use witha wide variety of available colorants. Furthermore, because the colorantreacts quickly with the coating compositions, the printed substrate doesnot require a separate curing step, but rather is fast-drying. Thisfast-drying characteristic provides for printed images that are“non-sticky,” thus allowing the printed textile substrate to be handledimmediately after printing, for example, to allow stacking. The treatedtextile substrate of the invention can also be used to prepare imageswith varying degrees of gloss, depending upon variations in pigment.

In addition to their water resistance, textile substrates treated with acoating composition of the invention are highly bleed-resistant (asevidenced by small dot size measurements, i.e., less wicking action),detergent-resistant and rub-resistant.

The various components of the coating compositions of the invention willnow be described.

1. COATING AGENTS

Coating agents in the coating compositions of the invention generallycomprise an azetidinium polymer, a guanidine polymer, a copolymer of anazetidinium monomer and a guanidine monomer, or a mixture of anazetidinium polymer and a guanidine polymer. In general, the coatingagent represents approximately 1 wt. % to 100 wt. %, typically 50 wt. %to 95 wt. %, preferably 70 wt. % to 95 wt. % of the coating compositionafter drying on a substrate.

a) Azetidinium Polymers

In one embodiment, the coating agent is an azetidinium polymer. An“azetidinium polymer” is a polymer comprised of monomeric subunitscontaining a substituted or unsubstituted azetedine ring (i.e., a fourmembered nitrogen-containing heterocycle). In general, the azetidiniumpolymers useful herein are composed of monomer units having thestructural formula (I):

in which R¹ and R² are independently lower alkylene, X⁻ is an anionic,organic or inorganic counterion, and Y¹, Y² and Y³ are selected from thegroup consisting of hydrogen, hydroxyl, halo, alkoxy, alkyl, amino,carboxy, acetoxy, cyano and sulfhydryl. Preferred suchpolymers arewherein R¹ and R² are methylene, X⁻ is selected from the groupconsisting of halide, acetate, methane sulfonate, succinate, citrate,malonate, fumarate, oxalate and hydrogen sulfate, Y¹ and Y³ areindependently hydrogen or lower alkyl, and Y² is hydrogen or hydroxyl.In particularly preferred azetidinium polymers herein, Y¹ and Y³ arehydrogen and Y² is hydroxyl.

The azetidinium polymer may be a homopolymer, or it may be a copolymer,wherein one or more non-azetidinium monomer units are incorporated intothe polymer structure. Any number of comonomers may be employed to formsuitable azetidinium copolymers for use herein; however, a particularlypreferred azetidinium copolymer is aminoamide azetidinium. Further, theazetidinium polymer may be essentially straight-chain or it may bebranched or crosslinked.

Azetidinium polymers can associate with colorant in two different ways.First, the azetidinium polymer can associate with colorant through anionic interaction, where the colorant provides anionic groups, such ascarboxy or sulfonate, that can ion-exchange with the polymer counterions(X⁻ in Formula (I), above), thus fixing the colorant to the textilesubstrate via an electrostatic-type interaction. Second, nucleophilicgroups present within the colorant can react with the azetidinium groupsof the polymer via a ring-opening reaction. A characteristicring-opening reaction of an azetidinium polymer of the invention may beillustrated as follows:

The colorant (◯-Nuc⁻) thus covalently bonds to the coating agent, toform a cross-linked coating agent-colorant complex. Colorant thusapplied to a coated textile substrate is rapidly and irreversibly boundto the textile substrate.

The percentage of reactive azetidinium groups in the polymer can beadjusted in a controlled manner to tailor the number of reactive groupsin the polymer. Azetidinium groups are insensitive to pH change;however, such groups are highly sensitive to the presence of anionic andnucleophilic species. In some cases, it may be desirable to adjust thereaction conditions used to prepare the azetidinium polymer (e.g., byraising the pH) to generate anionic groups within the polymer, whichthen participate in intramolecular crosslinking.

A preferred azetidinium polymer for use in the present invention isshown in Formula (II)

Commercially available such polymers include “AMRES®,” available fromGeorgia Pacific Resins, Inc., Atlanta, Ga., “KYMENE®,” from Hercules,Inc., Wilmington, Del., and “Polycup®,” also from Hercules, Inc. Theseazetidinium polymers are generally referred to aspoly(aminoamide)-epichlorohydrin (PAE) resins; such resins are typicallyprepared by alkylating a water-soluble polyamide containing secondaryamino groups with epichlorohydrin. Other suitable azetidinium polymerswill be known to those skilled in the art and/or are described in thepertinent texts, patent documents, and literature references; see, forexample, Moyer, et al., in WET STRENGTH IN PAPER AND PAPERBOARD, TappiMonograph Series No. 29, Tappi Press, Ch. 3, p. 33-37 (1965); Chan, inTAPPI WET AND DRY STRENGTH SHORT COURSE, Tappi Press, Atlanta, Apr.13-15, 1988; and Espy, in WET STRENGTH RESINS AND THEIR APPLICATION,Ed., Lock L. Chan, Tappi Press, Atlanta, Ga. (1994).

(B) Guanidine Polymers

In another embodiment, the coating agent is a guanidine polymer, alsotermed a “polyguanidine.” The guanidino group is extremely basic,possessing a pKa of about 12-13. Polyguanidines for use in the inventionare typically provided as acid salts wherein the imine nitrogen atomsare for the most part in protonated form.

In general, guanidine polymers useful as coating agents in the presentinvention are either homopolymers or copolymers. All guanidine polymersherein are comprised of recurring monomer units having the structuralformula

wherein R³ is hydrogen or lower alkyl and R⁴ is hydrogen, alkyl, alkoxy,or hydroxyl-substituted alkoxy. Preferably, R³ and R⁴ are hydrogen.Particularly preferred guanidine polymers for use herein are comprisedof monomer units having the structural formula (IV)

wherein n is an integer in the range of 1 to 10 inclusive, R³ ishydrogen or lower alkyl and R⁴ is hydrogen, alkyl, alkoxy, orhydroxyl-substituted alkoxy. Preferably, R³ and R⁴ are hydrogen.

A particularly preferred guanidine polymer for use in the methods andcompositions of the invention has the structure of formula (IV) whereinR³ and R⁴ are H and n is 6(3,12-diimino-2,4,11,13-tetraazatetradecanediimidamide), available underthe tradenames “BAQUACIL®” and “VANTOCIL®,” from Zeneca, Inc.

Polyguanidine polymers of the invention react electrostatically withanionic groups present in the dye via ion-exchange type interactions, torapidly and irreversibly bind anionic type dyes to print textilesubstrates coated with such polymers.

(C) Mixtures of Azetidinium Polymers and Guanidine Polymers

In another embodiment, the coating agent comprises a mixture of anazetidinium polymer and a guanidine polymer. The two polymers may bepresent in any suitable ratio relative to one another. The relativeamounts of polyguanidine and polyazetidinium can range from about 0.05%polyguanidine/99.95% polyazetidinium to 0.05% polyazetidinium/99.95%polyguanidine. The actual relative amounts of polyguanidine andpolyazetidinium will vary according to the composition of the ink to beused (e.g., the nature of the colorant in the ink), the nature of thetextile substrate, and other factors affecting the use of the polymers,such as the relative market price for each polymer. In general, it ispreferable to use a smaller amount of guanidine relative to azetidinium.

In this embodiment, it is important that the pH of the coatingcomposition be acidic, as the composition tends to gel at basic pH. Ifnecessary, then, an acid should be added to the coating composition toensure that the pH is below 7.0, preferably less than about 5.5, andmost preferably in the range of about 1.0 to 5.5. Suitable acids includesulfuric acid, hydrochloric acid, acetic acid, and the like.

Although it will be appreciated that any of a number of azetidinium orguanidine polymers can be used to prepare the coating compositions andcoated textile substrates described herein, a preferred polymer is apoly (aminoamide)-azetidinium polymer, e.g., a polyazetidiniumchloride-based polymer, such as a polyamide-polyamine-epichlorohydrinresin.

(D) Copolymers of Azetidinium Monomers and Guanidine Monomers

In another embodiment, the coating agent is a copolymer of anazetidinium monomer unit and a guanidine monomer unit. In general, theazetidinium monomer unit has the structural formula (I)

in which R¹ and R² are independently lower alkylene, X⁻ is an anionic,organic or inorganic counterion, and Y¹, Y² and Y³ are selected from thegroup consisting of hydrogen, hydroxyl, halo, alkoxy, alkyl, amino,carboxy, acetoxy, cyano and sulfhydryl. Preferred monomers are whereinR¹ and R² are methylene, X⁻ is selected from the group consisting ofhalide, acetate, methane sulfonate, succinate, citrate, malonate,fumarate, oxalate and hydrogen sulfate, Y¹ and Y³ are independentlyhydrogen or lower alkyl, and Y² is hydrogen or hydroxyl. In particularlypreferred azetidinium monomers, Y¹ and Y³ are hydrogen and Y² ishydroxyl. The guanidine monomer has the structural formula (III)

or the structural formula (IV)

wherein R³, R⁴ and n are as defined earlier herein.

The ratio of azetidinium monomers to guanidine monomers in thecopolymer, as well as the distribution of each monomer type in thecopolymer, can be varied according to a number of factors, and may be,for example, tailored for use with specific colorants having certaintypes of ionic and/or nucleophilic groups. The precise composition ofthe copolymer may also be varied to best accommodate the nature of thetextile substrate to be coated.

2. FILM-FORMING BINDERS

The textile coating compositions of the invention preferably include afilm-forming binder. By “film-forming binder” is meant a substance thatprovides for improved strength of a textile substrate upon applicationof the substance to the substrate. “Film-forming binders” used inconnection with the coating compositions of the invention include anyfilm-forming binder that is compatible with the coating agent and othercomponents of the composition. Exemplary film-forming binders include,but are not necessarily limited to: polysaccharides and derivativesthereof, e.g., starches, cellulosic polymers, dextran and the like;polypeptides (e.g., collagen and gelatin); and synthetic polymers,particularly synthetic vinyl polymers such as poly(vinyl alcohol),poly(vinyl phosphate), poly(vinyl pyrrolidone), vinyl-pyrrolidone-vinylacetate copolymers, vinyl alcohol-vinyl acetate copolymers, vinylpyrrolidone-styrene copolymers, and poly(vinylamine), and cationicfilm-forming binders such as quaternized vinylpyrrolidone-dimethylaminoethyl-methacrylate copolymer,dimethylaminoethyl-methacrylate-co-methyl methacrylate,polydiallyldimethyl ammonium chloride and quaternized aminoacrylatepolymers. The coating agents herein are themselves film-formingsubstances; however, it is generally desirable to use these coatingagents with additional film-forming substances.

Polysaccharide binders: Starches, as noted above, represent one categoryof suitable film-forming binders for use herein. Suitable starches maybe any of a variety of natural, converted, and synthetically modifiedstarches. Exemplary starches include, but are not necessarily limited tostarch (e.g., SLS-280 (St. Lawrence Starch)), cationic starches (e.g.,Cato-72 (National Starch), hydroxyalkylstarch, wherein the alkyl has atleast one carbon atom and wherein the number of carbon atoms is suchthat the material is water soluble, preferably from about 1 to about 10carbon atoms, such as methyl, ethyl, propyl, butyl, or the like (e.g.,hydroxypropyl starch #02382 (PolySciences, Inc.), hydroxyethyl starch#06733 (PolySciences, Inc.), Penford Gum 270 and 280 (Penford), andFilm-Kote (National Starch)), starch blends (see, e.g., U.S. Pat. No.4,872,951, describing a blend of cationic starch and starch treated withan alkyl or alkenyl succinic anhydride (ASA), preferably 1-octenylsuccinic anhydride (OSA)), and the like. The film-forming binder canalso be a synthetically produced polysaccharide, such as a cationicpolysaccharide esterified by a dicarboxylic acid anhydride (see, e.g.,U.S. Pat. No. 5,647,898). Additional saccharide binders includecellulosic materials such as alkyl celluloses, aryl celluloses, hydroxyalkyl celluloses, alkyl hydroxy alkyl celluloses, hydroxy alkylcelluloses, dihydroxyalkyl cellulose, dihydroxyalkyl cellulose, hydroxyalkyl hydroxy alkyl cellulose, halodeoxycellulose, amino deoxycellulose,dialkylammonium halide hydroxy alkyl cellulose, hydroxyalkyl trialkylammonium halide hydroxyalkyl cellulose, dialkyl amino alkyl cellulose,carboxy alkyl cellulose salts, cellulose sulfate salts,carboxyalkylhydroxyalkyl cellulose and the like). Still additionalfilm-forming binders of this type include dextran (e.g., dialkylaminoalkyl dextran, amino dextran, and the like), carrageenan, Karayagum, xanthan, guar and guar derivatives, (e.g., carboxyalkylhydroxyalkyl guar, cationic guar, and the like), and gelatin.

Additional exemplary film-forming binders include resins (e.g., such asformaldehyde resins such as melamine-formaldehyde resin,urea-formaldehyde resin, alkylated urea-formaldehyde resin, and the like), acrylamide-containing polymers (e.g., poly(acrylamide),poly(N,N-dimethylacrylamide), and the like),poly(alkyleneimine)-containing polymers (e.g., poly(ethyleneimine),poly(ethyleneimine) epichlorohydrin, alkoxylated poly(ethyleneimine),and the like), polyoxyalkylene polymers (e.g., poly(oxymethylene),poly(oxyethylene), ethylene oxide/propylene oxide copolymers, ethyleneoxide/2-hydroxyethyl methacrylate/ethylene oxide and ethyleneoxide/hydroxypropyl methacrylate/ethyleneoxide triblock copolymers,ethylene oxide-4-vinyl pyridine/ethylene oxide triblock copolymers,ethylene oxide-isoprene/ethylene oxide triblock copolymers,epichlorohydrin-ethylene oxide copolymer, and the like), etc.

Any of the above exemplary film-forming binders can be used in anyeffective relative amounts, although typically the film-forming binder,if present, represents approximately 1 wt. % to 40 wt. %, preferably 1wt. % to 25 wt. %, most preferably 1 wt. % to 15 wt. % of thecomposition, after drying on a textile substrate.

3. OTHER COMPONENTS OF THE TEXTILE COATING COMPOSITION

Additional coating composition components may include, but are notnecessarily limited to, inorganic fillers, anti-curl agents, oradditional conventional components such as a surfactant, plasticizer,humectant, UV absorber, light fastness enhancer, polymeric dispersant,dye mordant, optical brightener, fabric softener or leveling agent, asare comrnonly known in the art. Preferred additives are opticalbrighteners and fabric softeners, each of which generally representsapproximately 0.5 wt. % to 2.0 wt. % of the coating composition afterdrying on a substrate. Illustrative examples of such additives areprovided in U.S. Pat. Nos. 5,279,885 and 5,537,137. The coatingcompositions may also include a crosslinking agent, such as zirconiumacetate, ammonium zirconium carbonate, or the like, for intramolecularand/or intermolecular crosslinking of coating agent(s) in the coatingcomposition and/or a chelating agent such as boric acid. Additionalcomponents that may be desirable for use in the textile coatingcompositions of the invention will be known to those skilled in the artand/or described in the pertinent texts and literature.

The coating composition is preferably provided in an aqueous liquidvehicle, although small amounts of a water-soluble organic solvent maybe present. The aqueous liquid vehicle will generally be water, althoughother nonorganic compounds that are either water soluble or watermiscible may be included as well. It may on occasion be necessary to adda solubilizing compound during preparation of the coating composition sothat the components dissolve in the aqueous liquid vehicle, e.g., aninorganic base such as ammonia and/or an organic amine. Suitable organicamines include lower alkyl-substituted amines such as methylamine,dimethylamine, ethylamine, and trimethylamine, as well as ethanolamine,diethanolamine, triethanolamine, and substituted ethanolamines,typically lower alkyl-substituted ethanolamines such as N-methyl andN,N-dimethyl ethanolamines, and morpholine. Such compounds are alsouseful for bringing the pH into the desired range for basicformulations, and, if present, will generally represent not more thanabout 20 wt. % of the composition, and in most cases will represent notmore than about 10 wt. % of the composition.

Textile Substrates

In general, the textile coating compositions and printing methods of theinvention can be used with any textile substrate amenable to use withsuch coating compositions and methods. Suitable textile substrates foruse with the present invention include textiles having natural,synthetic, cellulose-based, or non-cellulose-based fibers or anycombination thereof. Exemplary textile substrates include, but are notlimited to, textiles having hydroxy group-containing fibers such asnatural or regenerated cellulosic fibers (cotton, rayon, and the like);nitrogen group-containing fibers such as polyacrylonitrile; natural orsynthetic polyamides (including wool, silk, or nylon); and/or fibershaving acid-modified polyester and polyamide groups. The substrates maybe additionally pre-treated or after-treated with resins or othersubstances compatible with the coating compositions and methods of theinvention, and may be finished or unfinished. The textile substrate mayalso be sized prior to application of the present coating compositions.Alternatively, the present coating compositions may be incorporated intoan external sizing process, so that sizing and coating is conducted in asingle step.

The fibers of the textile substrate may be in any suitable formcompatible with the selected printing process. e.g., loose yarns, orfabrics. Fabrics are a convenient and preferred form. The fibers may beblended with other fibers that are susceptible to treatment with acoating composition of the invention, or with fibers that may prove lesssusceptible to such treatment. The process may also be used withleather, vinyl and other natural or synthetic materials. Additionalexemplary substrates for use in the invention include polyester filmssuch as “MYLAR” flexible film, polysulfones, cellulose triacetates, andthe like. Coated transparent films are also contemplated.

Application of the Coating Compositions to Textile Substrates

Coated textile substrates, also referred to herein as “treated textilesubstrates,” can be prepared by any of a number of conventional coatingprocesses commonly employed in the art. In general, the coatingcomposition is applied to the textile substrate to provide a treatedtextile substrate in a manner that leaves the coating agent physicallyand chemically accessible to inks for reaction of the colorant-reactivecoating agent within the colorant contained in the ink. The term“coating” as used herein encompasses both a surface coating as well as acoating that has infiltrated the textile to some degree, so long as, inthe latter case, the coating agent is still accessible to colorant forprinting.

The textile coating composition is applied to a textile substrate toachieve a desired coating layer thickness and/or to achieve delivery ofa desired amount of coating composition to the textile substrate. Theamount of coating composition used will vary with a number of factors,including, for example, the absorptive nature of the substrate, the inkto be used in printing on the substrate, the printing application to beused, and the like. In general, the coating composition is applied in anamount that results in a coating representing approximately 0.5 wt. % to20 wt. % of the textile substrate after drying.

The coating is applied to at least one surface of the textile substrate,and may be applied to both a top and bottom surface of the substrate tofacilitate printing on opposing substrate surfaces. The coatingcomposition may also be applied by saturating a textile substrate. Aswill be appreciated by those skilled in the art, the coatingcompositions of the invention are applied by any suitable means, whichmay include continuous processes, application as a continuous film,padding, dipping, spraying, foam application, exhaust processes, or byusing a rod, roll, flexopress, blade, or air-knife coater.

The coating composition may be applied to the textile substrate as apretreatment, simultaneously with printing, or as an after-treatment.Preferably, the coating composition is applied to the substrate as apretreatment, i.e., prior to printing.

The coated textile substrate described herein possesses advantageousfeatures. For example, the coated textile substrate does not discolor oryellow. Additionally, the coating composition is compatible with avariety of textiles. Moreover, textile substrates coated with thecoating compositions described herein react rapidly with applied aqueouscolorants.

Preparation of Printed Images on Treated Textile Substrates

The coated textile substrates of the invention can be printed on usingany suitable inks and any suitable printing method, e.g., conventionalmethods of printing, digital printing (e.g., inkjet printing, includingdrop on-demand and continuous jet printing), and the like.

In general, aqueous inks are used in the preparation of a printed imageon the treated textile substrates of the invention. Aqueous inks for usein preparing a printed image may be any suitable ink having a colorant,e.g., a pigment, dye, or stain, having one or more reactive groupssuitable for reacting, either covalently or ionically, with acolorant-reactive component of a coating agent in the coating of thetreated textile substrate. The selection of the specific ink andcolorant will vary with colorant-reactive component of the coatingagent. For example, when the colorant-reactive component is anazetidinium group, the colorant has an anionic or nucleophilic group forreaction with the azetidinium group. When the colorant-reactivecomponent is a guanidino group, the colorant has an anionic group forreaction with the guanidino group. Thus, preferred colorants for use inprinting on a textile substrate coated with an azetidinium-containingcoating composition are those containing one or more nucleophiles, e.g.,having an amino, carboxy, sulfonato, thiosulfonato, cyano, hydroxy orsulfido group or the like. Preferred colorants for use in printing atreated textile substrate coated with a polyguanidine-containing coatingcomposition are those containing an anionic group, e.g., having acarboxy, sulfonato, thiosulfonato, cyano, halo, or phosphonato group orthe like.

The inks used in conjunction with the textile coating compositions ofthe invention may be inkjet inks. Water-soluble colorants in the inkjetinks may be acid dyes, direct dyes, basic dyes or dispersive dyes;preferred dyes are described in U.S. Pat. Nos. 5,425,805, 5,537,137, and5,441,561.

The selection of the aqueous based ink will depend upon the requirementsof the specific application, such as desired surface tension, viscosity,drying time, the type of textile substrate upon which the ink is to beapplied (printing medium), and the like. The aqueous liquid vehicle ofinks suitable for use in the invention will generally be water, althoughother nonorganic compounds which are either water soluble or watermiscible may be included as well. The colorant may be dissolved,dispersed or suspended in the aqueous liquid vehicle, and is present inan amount effective to provide the dried ink with the desired color andcolor intensity.

In some instances, the dye is contained in a carrier medium composed ofink and a water soluble organic solvent. For applications utilizing sucha carrier medium, representative solvents include polyhydridic alcoholssuch as polyethylene alcohol, diethylene glycol, propylene glycol, andthe like. Additional solvents are simple alcohols such as ethanol,isopropanol and benzyl alcohol, and glycol ethers, e.g., ethylene glycolmonomethyl ether, diethylene glycol monoethyl ether. Representativeexamples of water soluble organic solvents are described in U.S. Pat.No. 5,085,698 and U.S. Pat. No. 5,441,561.

Preferred colorants contained in the inks useful with the invention aredyes, including azo or “direct” dyes as well as dyes containing acidicgroups (e.g., carboxylate, phosphonate or sulfonate moieties), basicgroups (e.g., unsubstituted amines or amines substituted with 1 or 2alkyl, typically lower alkyl, groups), or both. Specific examples ofsuitable colorants include, but are not limited to, the following:Dispersol Blue Grains (Zeneca, Inc.), Duasyn Acid Blue (HoechstCelanese), Duasyn Direct Turquoise Blue (Hoechst Celanese),Phthalocyanine blue (C.I. 74160), Diane blue (C.I. 21180), Pro-jet Cyan1 (Zeneca, Inc.), Pro-jet Fast Cyan 2 (Zeneca, Inc.), Milori blue (aninorganic pigment equivalent to ultramarine) as cyan colorants;Dispersol Red D-B Grains (Zeneca, Inc.), Brilliant carmine 6B (C.I.15850), Pro-jet magenta 1 (Zeneca, inc.), Pro-jet Fast magenta 2(Zeneca, Inc.), Brilliant Red F3B-SF (Hoechst Celanese), Red 3B-SF(Hoechst Celanese), Acid Rhodamine (Hoechst Celanese), Quinacridonemagenta (C.I. Pigment Red 122) and Thioindigo magenta (C.I. 73310) asmagenta colorants; Dispersol Yellow D-7G 200 Grains (Zeneca, Inc.),Brilliant yellow (Hoechst Celanese), Pro-jet yellow 1 (Zeneca, Inc.),Pro-jet Fast Yellow 2 (Zeneca, Inc.), benzidine yellow (C.I. 21090 andC.I. 21100) and Hansa Yellow (C.I. 11680) as yellow colorants; organicdyes; and black materials such as carbon black, charcoal and other formsof finely divided carbon, iron oxide, zinc oxide, titanium dioxide, andthe like. Specific and preferred black colorants include Acid Black 48(Aldrich), Direct Black 58756 A (Crompton & Knowles), BPI MolecularCatalytic Gray (Brain Power), Fasday Cool Gray (Hunter Delator),Dispersol Navy XF Grains (Zeneca, Inc.), Dispersol Black CR-N Grains(Zeneca, Inc.), Dispersol Black XF Grains (Zeneca, Inc.), Disperse Black(BASF), Color Black FW18 (Degussa), Color Black FW200 (Degussa),Hostafine Black TS (Hoechst Celanese), Hostafine Black T (HoechstCelanese), Duasyn Direct Black (Hoechst Celanese), Pro-jet Black 1(Zeneca, Inc.) and Pro-jet Fast Black 2 (Zeneca, Inc.).

Printed Textiles

The invention also features a printed, treated textile substrateproduced using the methods and compositions described herein. Thetreated textile substrates of the invention can be printed using anysuitable printing method, e.g., conventional methods of printing,digital printing, particularly inkjet printing, including drop on-demandprinting and continuous jet printing, and the like. In one embodiment ofparticular interest, the treated textile substrates are printed by aninkjet printing method. In general, the printing process involvesapplying an aqueous recording liquid to a treated textile substrate inan imagewise pattern. Ink t printing processes are well known in theart; see, e.g., U.S. Pat. Nos. 4,601,777; 4,251,824; 4,410,899;4,412,224; and 4,532,530.

The compositions of the invention make it possible to print the treatedtextile substrates of the invention using printing methods that areconventionally used in connection with cellulosic paper substrates. Forexample, printing and/or copying process using dry or liquidelectrophotographic-type developers, such as electrophotographicprocesses, ionographic process, and the like, may be adapted forprinting the treated textile substrates of the invention. The treatedtextile substrates of the invention can also be printed on using aprocess for generating images that involves generating an electrostaticlatent image on an imaging member in an imaging apparatus, developingthe latent image with a toner, and transferring the developed image to atreated textile substrate of the invention. Electrophotographicprocesses are known in the art; see, e.g., U.S. Pat. No. 2,297,691.Ionographic and electrographic processes are also well known in the art,see, e.g., U.S. Pat. No. 3,611,419, 3,564,556; 4,240,084; 4,569,584;2,919,171; 4,524,371; 4,619,515; 4,463,363; 4,254,424; 4,538,163;4,409,604; 4,408,214; 4,365,549; 4,267,556; 4,160,257; and 4,155,093.

The printing process using treated textiles does not require a separatecuring step. For example, reaction of the colorant-reactive component ofthe coating agent in the coating composition with the colorant in theink can occur at room temperature. However, exposure of the printed,coated textile substrate to heat (e.g., using conventional heat pressprocesses) will speed the reaction of the dye with the coating agent.

After printing, the printed, coated textile substrates can be furthertreated using any compositions and processes that are compatible withthe coating agents and coated textile substrates described herein.

Characteristics of Printed Images

The printed, treated textile substrates as described herein interactrapidly and, in most cases, non-reversibly with a number of aqueousbased dyes, providing a versatile medium for use with a wide variety ofaqueous dyes. The printed, treated substrates are also water-resistantand bleed-resistant (as evidenced by small dot size measurements, i.e.,less wicking action) and maintain a high degree of brightness forextended periods of time. Printed images formed upon the treated textilesubstrate are also fast-drying. Moreover, the coating composition can beused to prepare images with varying degree of gloss, depending uponvariations in pigment.

Images printed upon a treated textile substrate of the type describedherein can be analyzed for any of a number of representative featuresusing standard analytical techniques to obtain measurements for opticaldensity, water-fastness, chroma and hue (via LAB graphs), dot size, andthe like. As can be seen on the basis of the results below, uponapplication of ink with an inkjet printer, substrates treated with avariety of coating compositions in accordance with the invention resultin superior print images which are clear, durable, highly luminant,non-feathered, and water-resistant and/or water-fast.

In addition, images printed on treated textile substrates according tothe present invention are also detergent resistant and/ordetergent-fast. The detergent to which the images are resistant includea variety of commercially available detergents, (e.g., anionicdetergents, cationic detergents, non-ionic detergents, amphotericdetergents, etc.). Anionic detergents to which the printed, treatedtextile substrates are resistant include, but are not necessarilylimited to, alkyl aryl sulfonates (e.g., linear alkyl benzenesulfonate), alkyl aryl condensates (e.g., DDB (dodecyl benzene)), longchain (fatty) alcohol sulfates (e.g., having a chain of 12 to 18 carbonatoms), olefin sulfates and sulfonates, alpha olefin sulfate andsulfonates, sulfate monoglycerides, sulphate ethers, sulfosuccinates,alkane sulfonates, phosphate esters, alkyl isothionates, and sucroseesters.

EXPERIMENTAL

The following examples are put forth so as to provide those of ordinaryskill in the art with a complete disclosure and description of how toprepare and use the compounds disclosed and claimed herein. Efforts havebeen made to ensure accuracy with respect to numbers (e.g., amounts,temperature, etc.) but some errors and deviations should be accountedfor. Unless indicated otherwise, parts are parts by weight, temperatureis in °C. and pressure is at or near atmospheric.

Also, in these examples, unless otherwise stated, the abbreviations andterms employed have their generally accepted meanings. Abbreviations andtradenames are as follows (note that suppliers of each material areindicated as well):

Amres=azetidinium polymer (Georgia Pacific);

Gaufquat-755=cationic film-forming binder (ISP);

Gum 280=starch (Penford);

ISP 937=polyvinylpyrrolidone-dimethylaminomethacrylate (ISP);

Polectron=styrene/poly(vinyl pyrrolidone) copolymer (Polectron 430, ISPTechnologies);

Polycup=azetidinium polymer;

PVOH=polyvinyl alcohol (Airvol 523S, Air Products);

PVP=polyvinyl pyrrolidone (Aldrich);

Sif=fumed silica (Aerosil MOX 170, Degussa);

Sip=precipitated silica (FK3 10, Degussa);

Tinopal=brightener (Ciba Additives);

Vantocil=3,1 2-diimino-2,4, 11,13-tetraazatetradecanediimidamide, 20%aqueous solution (Vantocil IB, Zeneca, Inc.).

All patents, patent applications, journal articles and other referencesmentioned herein are incorporated by reference in their entireties.

EXAMPLE 1 PolyAzetidinium-Based Textile Coatings

The following table summarizes exemplary textile coating compositions inaccordance with the invention, wherein the coating agent is anazetidinium polymer. Each of the representative formulations was used tocoat and/or saturate cotton and cotton/polyester blend fabrics, whichwere then printed on using an aqueous ink and an inkjet printer. Theprinted textile substrates so prepared were found to have the beneficialfeatures described herein, i.e., with respect to bleeding, wicking andbrightness of printed images, as well as water resistance and rubresistance.

TABLE 1 POLYAZETIDINIUM-BASED TEXTILE COATINGS Formulation StarchAzetidinium Binder Styrene/PVP Pigment Viscosity, No. (Gum 280)(“Amres”) (PVOH) (“Polectron”) 1:4 Sif:Sip % Solids cP pH 84-1 53 20 7.020.0 14.5 85-1 52.5 20 7.0 20.0 14.6 74-2 22 38 8.0 32.0 13.3 74-3 22 4010.0 28.0 13.3 335 3.82 74-4 10 50 10.0 25.0 13.3 79-1 13 50 11.0 26.016.3 3.75 71-2 22 36 9.4 32.8 25.3 3.74 76-1 22 38 6.0 2.0 32.0 13.3 3483.73 76-2 22 36 6.0 4.0 32.0 13.3 74-1 22 33 8.0 5.0 32.0 13.3 479 3.8676-3 22 34 6.0 6.0 32.0 13.3 286 3.73 77-3 22 35 5.0 6.0 32.0 13.3 77-222 34 5.0 7.0 32.0 13.3 250 3.73 72-2 22 33 5.0 8.0 32.0 23.1 3.74 78-222 33 5.0 8.0 32.0 14.1 667 4.0 77-4 22 38 10.0 10.0 20.0 13.1 3.79 79-235 10 10.0 10.0 35.0 18.8 4.10 77-1 27.5 47.5 12.5 12.5 10.8 3.75 78-122 33 5.0 8.0 32 15.4 182 6.70 90-1 23 30 10.0 35 14.5 90-2 23 30 10.035 14.7 90-3 23 30 10.0 35 13.4 90-4 23 30 10.0 35 14.5

EXAMPLE 2 PolyGuanidine-Based Textile Coatings

The following table summarizes exemplary textile coating compositions inaccordance with the invention, wherein the coating agent is apolyguanidine or an azetidinium polymer, or wherein the coating agentcomprises a mixture of a polyguanidine and an azetidinium polymer. Eachof the representative formulations was used to coat and/or saturatecotton and cotton/polyester blend fabrics, which were then printed onusing an aqueous ink and an inkjet printer. The printed textilesubstrates so prepared were found to have the beneficial featuresdescribed herein, i.e., with respect to bleeding, wicking and brightnessof printed images, as well as water resistance and rub resistance.

TABLE 2 POLYGUANIDINE AND/OR POLYAZETIDINIUM-BASED TEXTILE COATINGSFormulation Starch Azetidinium Polyguanidine Binder Styrene/PVP PigmentSolids No. (Gum 280) (“Amres”) (“Vantocil”) (PVOH) (“Polectron”) 1:4Sif:Sip (%) Tinopal pH 46-2 45 17 10 28.0 14.2 79-3 45 17 10 28.0 17.64.71 84-3 54 10 5 8 22.5 15.2 84-2 60 10 5 5 20.0 14.8 83-3 46 15 2 730.0 16.4 83-2 40 20 3 7 30.0 16.5 83-1 37 25 5 5 28.0 16.4 73-1 10 50 510 25.0 24.0 3.94 73-2 35 5 5 10 10 35.0 18.1 4.40 88-1 50 10 5 5 3014.5 6.61 88-2 50 10 5 5 30.0 14.5 6.62 89-3 25 10 10 5 5 40 16.2 5.089-2 38 12.4 4.8 9.5 4.8 28.6 14.3 1.90 88-3 55 10 5 5 23 14.0 2.0 89-140 13 5 10 30 13.8 2.0 51-5 60 40 12.5 52-1 50 50 13.3 55-2 71.4 14.36.0 55-3 85.5 17.1 5.4 51-4 25 25 50 20.0 53-4 90 10 6.0 53-1 73.7 26.34.8 53-2 54.5 22.7 22.7 5.5 54-4 71.4 14.3 14.3 6.6 57-1 71 14 14 6.6

EXAMPLE 3

Fabrics were treated with textile coating compositions of the inventionas follows:

(a): Fabric cotton was soaked in an aqueous formulation containing 2%DETA (diethylene triamine) solution, 0.1% fabric softener and 0.1%brightener, for 0.5 h and allowed to drip dry.

(b): Fabric cotton treated as in (a) was soaked in an aqueouscomposition containing a 5% solution of Polycup 172, 0.1% fabricsoftener and 0.1% brightener, for 0.5 h and allowed to drip dry.

(c): Fabric cotton was soaked in an aqueous formulation containing 2%DETA and 12.5% Polycup, for 0.5 h and allowed to dry.

(d): Fabric cotton was soaked in an aqueous formulation containing 2%DETA, 12.5% Polycup, and a pH-adjusting agent to bring the pH toapproximately 5. After 0.5 h, the fabric was removed and allowed to dry.

(e): Polycup 172, 8 g (64 ml), and ISP 937, 2 g (20 ml), were diluted inwater to provide a 5% solution. Fabric softener (0.1%) and brightener(0.1%) were added. Fabric cotton and 100% cotton were soaked in thissolution, removed after 0.5 h, and allowed to drip dry.

(f): Polycup 172, 8 g (6 ml), and Gaufquat 755, 2 g (10 ml) were mixedand diluted in water to provide a 5% solution. Cotton and fabric cottonwere soaked in the solution, removed after 0.5 h, and allowed to dripdry.

(g): Fabric cotton was soaked in a 1% polyethyleneimine solution for 15min, squeezed and then allowed to drip dry. The dried cloth was thensoaked in a 5% Polycup solution and allowed to drip dry after squeezing.

(h): Fabric cotton was soaked in 1% DETA solution, then squeezed andallowed to drip dry.

(i): Fabric cotton was soaked in a 5% aqueous solution of Polycup 172,0.1% fabric softener and 0.1% brightener.

(j): A 5% solution of Amres was made by diluting Amres HS 30 (30%solution). 0.1% each of fabric softener and brightener were added. Thesurfactant Surfinol FS 85 was added to the formulation as well.

(k): A formulation containing Polycup 172+ Gaufquat 755 (7:3) wasprepared and made slightly acidic. Nylon Banner material was soaked inthe solution and allowed to drip dry.

The treated fabrics were allowed to dry, and were then printed on usingan aqueous ink and an inkjet printer. The printed fabrics pre-treatedwith the compositions of the invention were found to be water-fast andbleed-resistant, with the printed images of superior quality withrespect to chroma and hue.

What is claimed is:
 1. A process for producing a treated textilesubstrate, comprising the step of applying to the surface of a textilesubstrate a coating composition containing a coating agent selected fromthe group consisting of (a) a mixture of an azetidinium polymer and aguanidine polymer, (b) a copolymer of an azetidinium monomer and aguanidine monomer, and (c) a poly(aminoamide)-epichlorohydrin resin. 2.The process of claim 1, wherein the coating agent comprises a mixture ofan azetidinium polymer and a guanidine polymer.
 3. The process of claim2, wherein the azetidinium polymer is comprised of monomer units havingthe structural fornulla

in which R¹ and R² are independently C₁₋₆ alkylene, X⁻ is an anionic,organic or inorganic counterion, and Y¹, Y² and Y³ are selected from thegroup consisting of hydrogen, hydroxyl, halo, alkoxy, alkyl, amino,carboxy, acetoxy, cyano, and suilfhydryl.
 4. The process of claim 3,wherein the guanidine polymer is comprised of monomer units having thestructural formula

wherein R³ is hydrogen or C₁₋₆ alkyl and R⁴ is hydrogen, alkyl, alkoxy,or hydroxyl-substituted alkoxy.
 5. The process of claim 4, wherein, inthe guanidine polymer, R³ and R⁴ are hydrogen.
 6. The process of claim3, wherein the guanidine polymer is comprised of monomer units havingthe structural formula

wherein n is an integer in the range of 1 to 10 inclusive, R³ ishydrogen or C₁₋₆ alkyl and R⁴ is hydrogen, alkyl, alkoxy, orhydroxyl-substituted alkoxy.
 7. The process of claim 6, wherein, in theguanidine polymer, R³ and R⁴ are hydrogen.
 8. The process of claim 3,wherein, in the azetidinium polymer, R¹ and R² are methylene, X⁻ isselected from the group consisting of halide, acetate, methanesulfonate, succinate, citrate, malonate, fumarate, oxalate, and hydrogensulfate, Y¹ and Y³ are independently hydrogen or C₁₋₆ alkyl, and Y² ishydrogen or hydroxyl.
 9. The process of claim 8, wherein the guanidinepolymer is comprised of monomer units having the structural formula

wherein R³ is hydrogen or C₁₋₆ alkyl and R⁴ is hydrogen, alkyl, alkoxy,or hydroxyl-substituted alkoxy.
 10. The process of claim 9, wherein, inthe guanidine polymer, R³ and R⁴ are hydrogen.
 11. The process of claim8, wherein the guanidine polymer is comprised of monomer units havingthe structural formula

wherein n is an integer in the range of 1 to 10 inclusive, R³ ishydrogen or C₁₋₆ alkyl and R⁴ is hydrogen, alkyl, alkoxy, orhydroxyl-substituted alkoxy.
 12. The process of claim 11, wherein, inthe guanidine polymer, R³ and R⁴ are hydrogen.
 13. The process of claim8, wherein, in the azetidinium polymer, Y¹ and Y³ are hydrogen and Y² ishydroxyl.
 14. The process of claim 13, wherein the guanidine polymer iscomprised of monomer units having the structural formula

wherein R³ is hydrogen or C₁₋₆ alkyl and R⁴ is hydrogen, alkyl, alkoxy,or hydroxyl-substituted alkoxy.
 15. The process of claim 14, wherein, inthe guanidine polymer, R³ and R⁴ are hydrogen.
 16. The process of claim13, wherein the guanidine polymer is comprised of monomer units havingthe structural formula

wherein n is an integer in the range of 1 to 10 inclusive, R³ ishydrogen or C₁₋₆ alkyl and R⁴ is hydrogen, alkyl, alkoxy, orhydroxyl-substituted alkoxy.
 17. The process of claim 16, wherein, inthe guanidine polymer, R³ and R⁴ are hydrogen.
 18. The process of claim1, wherein the coating agent is comprised of a copolymer of anazetidinium monomer unit and a guanidine monomer unit.
 19. The processof claim 18, wherein the azetidinium monomer unit has the structuralformula

in which R¹ and R² are independently C₁₋₆ alkylene, X⁻ is an anionic,organic or inorganic counterion, and Y¹, Y², and Y³ are selected fromthe group consisting of hydrogen, hydroxyl, halo, alkoxy, alkyl, amino,carboxy, acetoxy, cyano, and sulfhydryl, and the guanidine monomer unithas the structural formula

wherein n is an integer in the range of 1 to 10 inclusive, R³ ishydrogen or C₁₋₆ alkyl and R⁴ is hydrogen, alkyl, alkoxy, orhydroxyl-substituted alkoxy.
 20. The process of claim 19, wherein, inthe azetidinium monomer unit, R¹ and R² are methylene, X⁻ is selectedfrom the group consisting of halide, acetate, methane sulfonate,succinate, citrate, malonate, fumarate, oxalate, and hydrogen sulfate,Y¹ and Y³ are independently hydrogen or C₁₋₆ alkyl, and Y² is hydrogenor hydroxyl.
 21. The process of claim 1, wherein the coating compositionis aqueous.
 22. The process of claim 1, wherein the coating compositionfurther comprises a colorant.
 23. The process of claim 22, wherein thecolorant is a pigment.
 24. The process of claim 23, wherein the pigmentis selected from the group consisting of silica, titanium dioxide andcalcium carbonate.
 25. The process of claim 22, wherein the colorant isa dye.
 26. The process of claim 1, wherein the coating composition isapplied in an amount that results in a coating representingapproximately 0.5 wt. % to 20 wt. % of the textile substrate afterdrying.
 27. The process of claim 1, wherein the coating agent representsapproximately 1 wt. % to 100 wt. % of the coating composition, basedupon total solids weight of the coating composition after drying.
 28. Atextile substrate treated by the process of claim
 1. 29. A textilesubstrate treated by the process of claim
 2. 30. A textile substratetreated by the process of claim
 18. 31. A method for providing awater-resistant printed image on a textile substrate, comprising:applying to a textile substrate a coating composition comprised of acoating agent selected from the group consisting of (a) a mixture of anazetidinium polymer and a guanidine polymer, (b) a copolymer of anazetidinium monomer and a guanidine monomer, and (c) apoly(aminoamide)-epichlorolhydrin resin, thereby producing a treatedtextile substrate; and applying a colorant composition to the treatedtextile substrate, wherein the colorant composition contains a coatingagent reactive colorant having ionizable and/or nucleophilic groups. 32.A printed textile product prepared by the method of claim
 31. 33. Theprinted textile product of claim 32, wherein the printed image iswater-resistant and detergent-resistant.
 34. The process of claim 1,wherein the coating agent is a poly(aminoamide)-epichlorohydrin resin.35. The method of claim 31, wherein the coating agent is apoly(aminoamide)-epichlorohydrin resin.
 36. The process of claim 1,further including, prior to application of the coating composition,pretreating the substrate with a pretreatment agent.
 37. The process ofclaim 36, wherein the pretreatment agent is a resin.
 38. The process ofclaim 36, wherein the pretreatment agent is a sizing agent.
 39. Theprocess of claim 31, further including, prior to application of thecoating composition, pretreating the substrate with a pretreatmentagent.
 40. The process of claim 39, wherein the pretreatment agent is aresin.
 41. The process of claim 39, wherein the pretreatment agent is asizing agent.